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1 Jurnal f the Krean Ceramic Sciety Vl. 47, N. 3, pp. 249~255, DOI: /KCERS Optical Prperties f (V, Pr)-dped ZrSiO 4 Green Pigments Kyu-Ri PynG and Byung-Ha Lee Department f Material Science & Engineering, Myngji University, YngIn, , Krea (Received March 25, 2010; Revised April 8, April 12, 2010; Accepted April 19, 2010) ù v w g Ÿw p ³ Á w w œw ( ; , 4 12 ; ) ABSTRACT T investigate ptical prperties f (V, Pr)-dped ZrSiO 4 green pigments, samples were prepared by the ceramic methd using NaF and NaCl as mineralizers. They were characterized by X-ray diffractin, UV-Vis spectrscpy and Raman spectrscpy. The changes f clr in the samples during heating and effect f mineralizers were studied in terms f valence f the vanadium and prasedymium in the zircn matrix. (V, Pr)-dped ZrSiO 4 pigments give rise t green clratin in 800 C. The xidatin state f V and Pr ins f pigments in the glazed samples were cnfirmed by UV-Vis absrptin spectra. This absrptin spectra shwed three typical bands f trivalent Pr at the 445, 480~490, 592 nm due t f-f transitins and tw brad bands f 302~380, 400~500 nm due t f-d transitins f tetravalent Pr. Accrding t the increasing amunts f, the tw brad bands shwed decreasing intensity at 290, 640 nm due t d-d transitins f tetravalent V. Key wrds : ZrSiO 4 green pigments, Oxidatin state, Absrptin spectra, Raman mde assignment 1. üy ƒ g, ü, e y ƒ w»» ƒwš. g 1) 1948 vanadium zircn blueƒ š 1950 prasedymium zircn yellw 1960 irn zircn pinkƒ. y Ca- Cr-Si ƒ x m C-Zn-Al-Cr v x vgj t z w. Zr-Si-Pr y Zr- Si-V yw w. g j ù g p w» x. lj l 3) z w. 2) R. A. Eppler V-ZrSiO 4 f Marker Technique w NaF w in diffusin mdel Crrespnding authr : Byung-Ha Lee da5raa@naver.cm Tel : Fax : vapr transprt mdel w. Ÿy ƒ SiO 2 w ZrO 2 ù w š w ù w { Ÿy w w š w. z Demiray et al, M. Ocana et al, G. Mnrs et al ù š w 4-6) ƒ, e w š w. v g y Na 2 MO 4 NaCl w 1956 Kat Takashima w. M. Trjan, M. Ocana et al, J. A. Badenes et al, F. Bndili et al w w f Pr ƒ g ü e ƒ 14) ¾ y w š. 7-13) S. Parasuraman g v cdpant ù w e w w. ù g jš ƒ w ƒ w š w. ù V Pr c-dpingw w w g š w r. M-ZrO 2, SiO 2 wš Ÿy NaF, NaCl w š ù v cdping g w wš w. V 2, Ÿy w y» w. 249

2 ù v w g Ÿw p 250 Table 1. Crystalline Phase and L* a* b* Value f V and Pr c-dped Pigments with Cntents Change f V 2 and at 800 C P 1 P 3 P 5 P 6 V 0.1 Z(vs)m(vw) Z(vs)m(vw) Z(vs)m(w) L* a* b* V 0.13 Z(vs)m(w) Z(vs)m(w) L* a* b* *NaF: 0.5 ml%, Hlding time : 3 h *Peak intensity: vs(very strng), m(medium), w(weak), vw(very weak) *Crystalline phase : Z: zircn, m: mnclinic ZrO 2 * V : V 2 (ml%), P: (%) 2. x 2.1. ù v cdping g w w» w p M-ZrO 2 (Yakuri) SiO 2 (Duksan) w. p prasedymium(iii, IV) xide(alfa Aesar), vanadium pentxide(junsei), Ÿy NaX (X=F, Cl)(Duksan) w., ZrO 2 SiO 2 mle yww z V 2 0.1~0.13 ml%, 1~6%, NaF NaCl 0~0.5 ml% ü ƒw g yww. ƒƒ 600 ~ 800 C 3 C ù ƒ w w w š, ƒƒ 3 w p w y w» w XRD(Shimadzu, XRD 7000) w. 2θ 20~70 scanning rate 10 /m d w š step size 0.2 w. g (αzrsio 4 =I ZS(200) +I M(11 ) +I M(111) +I T(111) ) 2θ 26~32 1 ùkù 4 p peak - ZrSiO 4 (200), (Mnclinic) M-ZrO 2 (11, 111) and (Tetragnal) T-ZrO 2 1 (111) w w. 15) w p V, Pr ƒ y w» w UV-Vis spectrscpy (Shimadzu, UV-2410 PC) w. w z w 1260 C w v 200~800 nm absrptin mde d w. CIE L * a * b * t w U.V PC ptical clr analysis sftware (P/ N ) w eyw. g V-O bnding mde y wš dphantƒ g raman spectra e w» w Raman spectrscpy (Dimentin D2, Lambda Slutin, Inc, U.S.A.) w. Raman spectrum vectr raman prve(rp532-us) w semicnductr 532 nm laser d w spectral reslutin 3cm -1 w. w p mw š w w V Pr ƒƒ e w r. w g d w SK 8 šy n Ÿk z w š, KNaO CaO Al 2 O SiO MgO BaO ƒƒ v z 10% ƒw 4 4cm k x r w. electric furnace 3 C/min 1260 C¾ wš 30 w z þw. 3. š 3.1 X-ray diffractin V 2 w y y V 2 w g w V 2 ƒ g e w. V 2 0.1, 0.13 ml% w ƒƒ1, 2, 3, 4, 5, 6% ƒw 800 C 3 w w w. w y Table 1 ùkü. Ÿy NaF 0.5 ml% ƒw w. g XRD vj ql j. ƒ ƒw 2 M-ZrO 2 ƒ š g w. ƒ g j w ù, Table 1 L* a* b* j w Ÿy w y y V 2 w w w. V ml% 6% ƒ w kw Ÿy y g e w. g w 47«3y(2010)

3 251 ³ Á w Fig. 1. XRD patterns f different cntents f mineralizers in (V, Pr)-dped ZrSiO 4 pigments at 800 C(V ml%, 6%) Z: zircn, m: mnclinic ZrO 2, C: cristbalite. Fig. 3. XRD patterns f different temperatures and cntents f mineralizers in (V, Pr)-dped ZrSiO 4 pigments.(v ml%, 6%) Z: zircn, m: mnclinic ZrO 2 C: cristblite, S: Na 2 ZrSiO 4, N: NaCl, P: Pr 8 Si 6 O 24. Fig. 2. Zircn fractins with different cntents f mineralizers(naf/nacl) in (V, Pr)-dped ZrSiO 4 pigments at 800 C(V ml%, 6%). (Fe, Pr, V) Ÿy. 16) w y w NaF NaCl w g, V 2 w w NaF w g ƒ w. V ml%, 6%, NaF 0.5 ml% ƒw kw NaCl ƒ y 800 C 3 w w w. w y Figs. 1 2 ùkü. NaF 0.5 ml% w w w g 86% w NaCl 0.5 ml% w w w XRD g 62% w. NaF 0.3, NaCl 0.2 ml% w w w 89% ƒw š, NaF 0.2, NaCl 0.3 ml% ƒw g 91% ƒ ùkû. m-zro 2 5.4% ƒ û. x ù v w g w w Ÿy NaF NaCl wì w z ù kû, g y j Ÿy ƒ NaF 0.2, NaCl 0.3 ml%. (V, Pr)-dped g w w NaF NaCl ƒ g e w. V ml%, 6%, NaF 0.2, NaCl 0.3 ml% ƒ w NaF 0.3, NaCl 0.2 ml% ƒ w 600, 700, 800 C 3 w w w. Fig. 3 ùkü. NaF NaCl œ 680 C š g» w. 16) Fig C NaF NaCl œ» NaCl Na 2 ZrSiO 4, Pr 8 Si 6 O 24 m-zro 2. g 700 C y» w. NaCl 0.2 ml% ƒ g w. NaCl 0.3 ml% g x ƒw ùkü» w ù m-zro C NaF 0.2, NaCl 0.3 ml% ƒw w g w š w yellwish green w. Na 2 ZrSiO 4 š Pr 8 Si 6 O 24. V 2 w g w w g ƒ V ml%, w wz

4 ù v w g Ÿw p 252 Table 2. L* a* b* Value and Munsell Clr Ntatin in Glazed Samples f Synthesized (V, Pr)-dped Pigments at 800 C fr 3 h V 2 (ml%) (%) M (ml%) L* a* b* H V/C Clr NF B 6.1/5.0 Light greenish blue " 2 " BG 6.7/3.4 Light bluish green " 3 " G 7.0/2.9 Light yellwish green " 4 " GY 7.4/4.5 Light greenish yellw " 6 NF Y 7.6/7.0 Greenish yellw " " NF 0.3 NC GY 6.9/4.0 Yellwish green " " NF 0.2 NC GY 6.7/3.2 Mderate yellwish green " " NC BG 5.9/3.5 Light bluish green *M : mineralizers NF :NaF NC:NaCl 6%, NaF 0.2, NaCl 0.3 ml%. NaF NaCl ƒ g j w p 700 C NaCl g j ùkû. 3.2 Optical prperties Clr Table 2 V 2,, NaF, NaCl w 800 C 3 w g w w. w Ÿy ƒ» w UV-Vis spectrscpy d w CIE L * a * b t w * eyw. Table 2 ùkü. V ml%, NaF 0.5 ml% ƒw ƒ ƒƒ 1, 2, 3, 4, 6% ƒ g 2% l (b* : 4.43)» w y (b* : 9.27 / 32.76) w. g ü t ü ù ü v c-dping ùkù yw w. V ml% 6% ƒw Ÿy ƒ y g w y w. NaF 0.5 ml% ƒw w w w y ùkü. NaF ƒ 0.3 ml% jš NaCl 0.2 ml% ƒw w. NaCl ƒ 0.3 ml% ƒ j a* 13.89, b* ƒ ƒw. ù NaCl 0.5 ml% ƒw w w (a* : 17.37, b* : 2.63) w. g ù v ƒ y j. x (mderate yellwish green) Ÿy NaF NaCl ƒ y. g Ÿy ƒ w Fig. 4. Optical absrptin spectras f a glazed sample with (V, Pr)-dped ZrSiO 4 pigments(v 2 0.1, NaF 0.5 ml%) accrding t different cntents f at 800 C(3 h). j w q UV-Vis absrptin spectra V 2 w g w w Ÿy ƒ y V Pr ƒ» w UV-Vis spectrscpy w. Figs. 4~6 Table 3 ùkü. Fig. 4 V ml%, NaF 0.5 ml% ƒw ƒƒ 1, 2, 3, 4% ƒw 800 C 3 w w w U.V-Vis spectra. ƒw ùkü 4+ V p 13) 290, 640 nm ƒ w š, y ùkü Pr 3+ (445, 18,19) 17) 480~490, 592 nm) Pr 4+ (302~380, 400~500 nm) p ƒ w. Pr 3+ p Pr e» y 4+ ù, nm wì ƒ ƒwš. Fig. 5 V ml%, 6% wš Ÿy ƒ y 700 C 47«3y(2010)

5 253 ³ Á w Fig. 5. Optical absrptin spectras f a glazed sample with (V, Pr)-dped ZrSiO 4 pigments(v ml%, 6%) accrding t different cntents f NaF and NaCl at 700, 800 C fr 3 h. Fig. 6. Raman spectras f ZrSiO 4 pwder and cmmercial zircn pigments. 800 C 3 w w w U.V-Vis spectra. w 800 C 4+ V w Ì Pr Pr p ƒ ƒw š, NaF 0.2, NaCl 0.3 ml% ƒw 800 C w w ƒ ƒ yw mderate yellwish green w. ƒ ë y ywš p q ƒ ë. w w ƒ ùk ùš ë. g ü 4+ V d- d wš. Pr 3+ d p f-f w w» f 4+ ùkü. Pr f-d w. g ü w 4+ V 4+, Pr 3+, Pr y w Table 3 ùkü. (1) visible spectrum frm 400 t 700nm ƒ Ÿ vilet-blue 400~500 nm t 1g f 18)» w 4+ Pr ƒ. Blue 445 nm Blue-green 480~ 490 nm, yellw 592 nm ƒƒ P 1, H P 0, H 4 1D 2» w 4 ƒ. k 3 H P 2, P 1, P 0, 1D 2» k w 3+ Pr p 17) G. D. A. Licciulli et al w y ew. Red 640nm 4+ V p 2 B 2 1 E 5)» w g t. x w w ƒ 400 ~ 500 nm 4+ Pr 445, 480 ~ 490, 592 nm Pr 4+ p wì 3+ ƒw š, 640 nm V p w. (2) Ultravilet regin frm 200 t 400 nm H 4 3 P 2, 3H 4 Ultravilet 290 nm 2 B 1 2 A 1 5)» w 4+ V ƒ, ƒ w t w. 302~380 nm Pr p 4+ 2t 2g f 18)» w V 4+ q w w yw Raman spectra w w (V, Pr)-dped g raman Table 3. Summery f the Absrptin Bands and Assignments f Sample with (V, Pr)-dped ZrSiO 4 Pigments(V ml%, 6%) accrding t Different Cntents f NaF and NaCl at 800 C(3 h) Valence state Band Assignments Wavelength (nm) ~ ~ Pr 3+ f-f transitin 17) 3 H P 2 H P 1 H 4 3 P 0 3H 4 1 D 2 w wz Pr 4+ Wavelength (nm) 302~ ~500 V 4+ f-d transitin 18,19) 2t 2g G f t 1g G f Wavelength (nm) d-d transitin 4) 2 B 1 G 2 A 1 2B 1 G 2 E

6 ù v w g Ÿw p 254 Table 4. Assignment f Raman Vibratinal Mdes in Synthesized (V, Pr)-dped Zircn Pigments and Cmmercial Zircn Pwder Cmpared with thse Observed fr tgether with Cmmercial Zircn Pigments (V, Pr) c-dped SZP (V, Pr) c-dped CZSP Pr-dped CZSP V-dped CZSP ṽ ṽ ṽ ṽ ṽ Cmmercial ZrSiO 4 Pwder /cm -1 /cm -1 /cm -1 /cm -1 /cm -1 Mde Assignment 20,21) Zircn B 1g Si-O v Zircn A 1g Si-O v V-O Zircn B 1g V-O Zircn B 1g Zircn E g Si-O v V-O Zircn E g Zircn E g External mde(rt.) Zircn E g External mde(trans.) *SZP : Synthesized ZrSiO 4 Pigment / CZSP : Cmmercial ZrSiO 4 Pigment mde y w» w w. g q ƒ š g w w g w Fig. 6 Table 4 ùkü. g q» w 1005(B 1g ), 972 (A 1g ), 401(E g )cm wavenumber Si-O -1 stretching mde w vj ƒ š 21) w. External mde 222 (E g ), 198 (E g ) peak 353 (E g )cm g p vjƒ -1. V-dped pigment spectra ƒƒ 950(v 1, stretching), 473(v 4, bending), 386(v 2, bending) cm -1 V-O mde ƒ 20). ù g x g raman spectra ql, v y ù v g m-zro 2 p vjƒ. v ƒ ƒw g û XRD ew. V ml%, 6%, NaF 0.5 ml% ƒw NaCl ƒ y 800 C 3 w w w. Ÿy ƒ raman spectra» w w d w Fig. 7 ùkü. y NaF 0.2, NaCl 0.3% ƒw w w Si-O stretching mde 21) p vjƒ 1005 cm -1 (B 1g ) y š, 865, 801, 789, 687,437, 353, 223 cm g p vj ƒ x -1. NaCl NaF ƒƒ 0.5 ml% w w w 950(v 1, stretching) 972 cm -1 (A 1g ) vj ratiƒ. Fig. 7. Raman spectras f V ml%, 6% dped zircn green pigments accrding t different cntents(ml%) f mineralizers(naf/nacl) at 800(3h). Z: Zircn, M: M-ZrO cm -1 V-O vibratin mde p vj ƒ ùkû. Table 4 ùkü y (V, Pr)-dped g 1005, 972, 950, 625, 472, 434, 353, 224 cm -1 raman active mde g p vjƒ y. 4. ù v cdpingw g š w w. V 2, NaF NaCl ƒ y w Ÿy ƒ g e w. w g ü V, Pr ƒƒ e w w. 47«3y(2010)

7 255 ³ Á w (1) (V, Pr)-dped g w, V ml%, 6% NaF 0.2, NaCl 0.3 ml% ƒw 800 C 3h w w w, w e L* 67.51, a* 13.89, b* (2) V ml%, 6% ƒw NaF 0.2, NaCl 0.3 ml% ƒw w w g 91%, Ÿy NaF NaCl w g g. w NaCl ƒ w. (3) w UV-Vis V in 4 k + ƒ ƒw vj w. Pr in 3+ w k œ w. Pr 445, 480~490, 592 nm, Pr 302~380, 400~ 500 nm p vjƒ š ƒ ƒw ƒw. (4) w Raman , 972, 950, 625, 472, 434, 353, 224, 198 cm zircn active mde cm V-O bnding mde y w. Acknwledgments This wrk was supprted by Krea Science and Engineering (KOSEF) grant funded by Krean Gvernment (MOST) (N. ROA ). REFERENCES 1. A. García, M. Llusar, J. Calb, M. A. Tena, and G. Mnrós, Lw-Txicity Red Ceramic Pigments fr Prcelainised Stneware frm Lanthanide Cerianite Slid Slutins, Green Chemistry, 3 [5] (2001). 2. R. Munz, N. Mas, B. Julian, F. Marquez, H. Beltran, P. Escriban, and E. Crdncill, Envirnmental Study f Cr 2 O 3 Al 2 O 3 Green Ceramic Pigment Synthesis, J. Eur. Ceram. Sc., 24 [7] (2004). 3. R. A. Eppler, Mechanism f Frmatin f Zircn Stains, J. Am. Ceram. Sc., 53 [8] (1970). 4. T. Demiray, D. K. Nath, and F. A. Hummel, Zircn-Vanadium Blue Pigment, J. Am. Ceram. Sc., 53 [1] 1-4 (1970). 5. M. Ocana and A. R. Gnzalez-Elipe, Spectrscpic Studies n the Lcalizatin f Vanadium(IV) in Vanadium Dped Zircn Pigments, J. Am. Ceram. Sc., 81 [2] (1998). 6. G. Mnrs, J. Carda, M. A. Tena, and P. Escriban, Different Kinds f Slid Slutins in the V 2 -ZrSiO 4 -NaF System by Sl-Gel Prcesses and their Characterizatin, J. Eur. Ceram. Sc., 11 [1] (1993). 7. C. A. Seabright, Yellw Pigments fr Ceramic Ware, US Patent 2,992,123 (1961). 8. E. Kat and H. Takashima, Study f Zircn Pigments- Vanadium Blue, Rep. Gv. Ind. Res. Inst, Nagya, 4 [2] (1956). 9. M. Trjan, Synthesis f Yellw Pigments, Dyes and Pigments, 9 [4] (1988). 10. M. Ocana, A. Caballer, A. R. Gnzalez-Elipe, and P. Tartaj, C. J. Serna, Valence and Lcalizatin in Pr-dped Zircn, J. Slid State Chem., 139 [2] (1998). 11. M. Ocana, A. Caballer, A. R. Gnzalez-Elipe, P. Tartaj, C. J. Serna, and R. I. Merin The Effects f the NaF Flux n the Oxidatin State and Lcalisatin f Prasedymium in Pr-dped Zircn Pigments, J. Eur. Ceram. Sc., 19 [5] (1999). 12. M. Shyama, H. Nasu, and K. Kamiya, Preparatin f Rare Earth-Zircn Pigments by the Sl-Gel Methd, J. Ceram. Sc. Jpn., 106 [3] (1998). 13. M. Llusar, J. B. Vicent, J. Badenes, M. A. Tena, and G. Mnrs, Envirnmental Optimisatin f Blue Vanadium Zircn Ceramic Pigment, J. Eur. Ceram. Sc., 19 [15] (1999). 14. S. Parasuraman, Investigatin f Zircn and Cerium Sulphide Based Inrganic Pigments, pp , Prject Reprt, Dept. Metal. Mater. Eng., India, Y. Kann, Thermdynamic and Crystallgraphic Discussin f the Frmatin and Dissciatin f Zircn, J. Mater. Sci., 24 [7] (1989). 16. K. R. Pyn and B. H. Lee, The Influence f Firing Cnditins n the Clr Prperties f Pr-ZrSiO 4 Pigments Synthesized using Rice Husk Ash, J. Kr. Ceram. Sc., 46 [4] (2009). 17. G. De A. Licciulli and M. Nacucchi, Unifrmly Dispersed Pr +3 Dped Silica Glass by the Sl-Gel Prcess, J. Nn- Crys. Slid., 201 [1] (1996). 18. H. E. Hefdraad, Charge-Transfer Spectra f Tetravalent Lanthanide Ins in Oxides, J. Inr. Nucl. Chem., 37 [3] (1975). 19. D. Pawlak, Z. Frukacz, Z. Mierczyk, A. Suchcki, and J. Zachara, Spectrscpic and Crystalgraphic Studies f YAG:Pr 4+ Single Crystals, J. Ally. Cmp., 275 [2] (1998). 20. D. De Waal, A. M. Heyns and G. Pretrius, Raman Spectrscpic Investigatins f ZrSiO 4 :V 4+, the Blue Zircn Vanadium Pigment, J. Ramans. Spec., 27 [4] (1996). 21. V. Presser and C. Gltzbach, Metamictizatin in Zircn : Raman Investigatin Fllwing a Rietveld Apprach, J. Ramans. Spec., 40 [5] (2009). w wz